Mechanical Properties and Microstructure of Mg-Al-Zn-Si-base Alloy

Materials Transactions, Vol. 44, No. 4 (2003) pp.
458 to 462
Special Issue on Platform Science and Technology for Advanced Magnesium Alloys, II
#2003 The Japan Institute of Metals
Mechanical Properties and Microstructure of MgAlZnSi-base Alloy

Yuan Guangyin1;2 * , Liu Manping1 , Ding Wenjiang1 and Akihisa Inoue2
1
2
Light Alloy Net Forming National Engineering Research Center, Shanghai Jiaotong University, Shanghai 200030, P.R.China
Institute for Materials Research, Tohoku University, Sendai 980-8579, Japan
Magnesium alloys containing Mg2 Si particles, as a promising low cost heat-resistant magnesium alloy for automobile engine applications,
are attracting more and more attention of both material scientists and design engineers. Renement of the Chinese script Mg2 Si particle is a key
for using this kind of alloy in sand casting or permanent mould casting. In the present work, a new type of heat-resistant magnesium alloy with
low cost based on MgAlZnSi was developed. The eect of Sb addition and mischmetal (MM, a mixture of rare-earth, RE elements)
microaddition to a MgAlZnSi alloy was investigated systematically from the viewpoints of microstructure, solidication process,
mechanical properties and corrosion resistance. Microstructure observation revealed that Sb promoted the formation of ne polygonal type
Mg2 Si particles by providing the nucleation sites. Meanwhile, the grain sizes of modied MgAlZnSiSb alloy are much ner than those of
base alloy. Such improved microstructure brings about the signicant improvement in tensile properties, toughness and creep resistance at
elevated temperatures up to 200 C, which is superior to or comparable to AE42 alloy. Moreover, the corrosion resistance of the new alloy is
improved signicantly by the MM microaddition.
(Received October 10, 2002; Accepted January 20, 2003)
Keywords: microstructure, mechanical properties, creep, corrosion resistance, magnesium alloy
1.
Introduction
The growing demand for more fuel-ecient vehicles to

reduce energy consumption and air pollution is a challenge
for the automotive industry. The characteristic properties of
magnesium alloys, low density, high strength stiness to
weight ratio, good damping capacity and diecastability, and
recycling potential make it the ideal candidate for heavier
materials (steel, aluminum) to reduce the weight of the car.
The widely used magnesium alloys are MgAl series, such as
AZ91 and AM60, which have excellent castability, good
mechanical properties at room temperature and low cost.
However, the use of these magnesium alloys have been
limited because of their poor heat resistance.1) The previous
investigation2) showed that the grain boundary sliding is an
important part of the deformation mechanism at elevated
temperatures in MgAl based alloys. Therefore, to improve
heat resistance in MgAl based alloy, it seems an eective
method to develop an alloy containing thermal stable
intergranular phases, which can suppress the grain boundary
sliding.
Recent studies indicate that addition of silicon to MgAl
Zn alloy can achieve substantial increases in strength,
toughness, etc. because Mg2 Si formed by the addition of Si
is the substantially eective strengthening particles, which
exhibit a high melting temperature (1085 C), low density
(1.9 g/cm3 ), high elastic modulus (120 GPa), and a low
thermal expansion coecient (7:5 106 C1 ).3) However,
the magnesium alloys containing Si are only limited to the
diecasting, which has a rapid solid rate. Mg2 Si compounds
are prone to forming undesirable coarse Chinese script under
conventional (or slower) solidication process. To use of
magnesium alloys containing Mg2 Si particles for sand
casting or permanent mould casting, microstructural rene*To
whom correspondence should be addressed. Current address: Inoue

Laboratory, Institute for Materials Research, Tohoku University, Sendai
980-8577, Japan. E-mail: gyyuan@imr.tohoku.ac.jp
ment should be achieved.

It has been reported that the as-cast microstructure of Mg
alloys containing Mg2 Si particles could be rened by P or Ca
addition.4) However, addition of phosphor can produce
ignition and result in large quantity of sick smoke. In recent
studies,5) we found a more eective modier of Sb than Ca in
MgAlZnSi alloys. This paper reports the results of our
preliminary experiments on the eects of Sb and MM
simultaneous additions on the microstructural development,
tensile strength, creep properties and corrosion resistance of
Mg5Al1Zn1Si alloy obtained by a permanent mould
gravity casting process.
2.
Experimental Procedure
Three alloys of which the compositions are listed in

Table 1 were prepared in mild steel crucible under the
protection of mixed gas of CO2 /0.5%SF6 using commercial
stock. Tensile specimens with a gauge section of 15 mm
3:5 mm 2 mm were cut by electric spark machining from
the bottom of ingots. Before testing all the specimens were
solution heat-treated at 410 C for 10 hours, water quenched,
and then aged at 200 C for 2 hours. All specimens for
microstructural characterization were cut from the same
positions on the ingots at 10 mm from the castings. Phases in
the Mg5Al1Zn1SiX alloys were analyzed by D/MaxIII
A-12KW-Cu type XRD analyzer operated at 40 kV and
120 mA. Chemical analysis of the cast experimental alloys
was performed by inductively coupled plasma (ICP). The
electropolished samples were examined in a Philip-505
scanning electron microscope equipped with an energy
dispersive X-ray spectrometer (EDS) to investigate the
microstructures and second phases in the alloys. The grain
size was determined using a line intercept method from a
large number of non-overlapping measurements.

Table 1
Alloy code
Mg
Al
459
Chemical composition of the alloys (mass%).

Zn
Si
Sb
Mn
Re
Grain size (mm)
Mg5Al1Zn1Si
Bal.
5.1
0.93
0.72
134 5
Mg5Al1Zn1Si0.5Sb
SJTU-HM1
Bal.
Bal.
5.0
5.0
0.95
0.90
0.70
0.71
0.45
0.40
0.20
68 5
70 5
AZ51
Bal.
5.0
0.80
0.20
AE42
Bal.
4.0
0.20
2.5
AZ91
Bal.
9.0
0.80
0.20
3.
Results and Discussion
3.1 Microstructure
The typical microstructure of the permanent mould cast
Mg5Al1Zn1Si based alloys is illustrated in Fig. 1. The
microstructure consisted of Chinese-script type Mg2 Si
particles with interdendritic Mg17 Al12 phases in matrix (Mg). When the as-cast specimens of the alloys were solution
treated at 420 C for 10 hours (T4 condition), almost all of
phase dissolved in the matrix and only Chinese-script type
Mg2 Si particle existed, as shown in Fig. 1(b), which indicated
that Mg2 Si has excellent thermal stability at elevated
temperatures. With the addition of Sb, two microstructural
changes can be observed clearly: (1) morphology of the
Mg2 Si particles changed from coarse Chinese script shape to
the ne polygonal shape. (2) the average size of grain
decreased from 134 to 68 mm (Figs. 1(b) and (c)). With the
mischmetal microaddition to Mg5Al1Zn1Si0.5Sb alloy,
the microstructure was not inuenced obviously. The renement may be due to the formation of lots of nely distributed
polygonal type Mg2 Si particles in the interface of liquid-solid
former during solidication.
Figure 2 is the XRD results of Mg5Al1Zn1Si0.5Sb
alloy. It is recognized peaks from Mg3 Sb2 phase in the Sbcontaining alloys.
3.2 Mg2 Si phase heterogeneous nucleation
Figure 3(a) shows micrograph of Mg2 Si particles in the
alloy containing 0.5Sb. It is interesting that Mg2 Si particles
contain small particles inside (labeled A), which presumably act as nucleation sites for Mg2 Si particles. Figure 3(a)
shows a typical result on crystallization center in the Sbcontaining alloy obtained by magnied secondary electron
image (SEI) of nucleus. Figure 3(b) shows the EDS spectra
for the nucleus. It shows that the nucleus is enriched with Mg,
Sb and Si. Combining the information from XRD and EDS
spectrum shows that the nature of nucleus is possible to be
Mg3 Sb2 .
In classical nucleation theory, nucleating can be facilitated
when the foreign particle displays a small lattice mismatch
(<6%) with the nucleating solid phase.6) The results of
calculation for some possible crystallographic orientations
for Mg2 Si nucleation on the Mg3 Sb2 particles show that
when the orientation relationship between Mg2 Si phase and
Mg3 Sb2 phase is 0001Mg3 Sb2 k 111Mg2 Si , the planar disregistry is the lowest (5.1%).5) Therefore, Mg3 Sb2 can act as
the heterogenerous nucleation for the Mg2 Si phase by this
orientation relationship.
3.3 Solidication process of MgAlZnSi-base alloys

Figure 4 shows a typical cooling curve for the Mg5Al
1ZnX based alloys under a cooling rate of 0.5 C/s. From the
curves of solidication, the following information could be
obtained: the practical temperature of the liquid metal at the
moment of entry to the mold was 648 C and 621 C
respectively, which was measured with a high sensitivity
thermocouple. The wall of mold cavity chilled the liquid
metal, causing the temperature of the liquid metal to rapidly
drop. A little platform appeared in the curve at about 616 C
for AZ51 and 606 C for SJTU-HM1 (The liquidus temperature of SJTU-HM1 is lower by 10 C than that of AZ51, which
may be benecial to the castability). With the decrease of
temperature, the liquid metal starts to solidify. Owing to the
high melting point of Mg2 Si particles, the Mg2 Si primarily
precipitated. Followed by the onset of Mg() formation, and
then the further growth of Mg2 Si phase and Mg() phase and
ends at 407 C (another platform, as arrowhead shown in
Fig. 4), which is actually the non-equilibrium eutectic
temperature for L!Mg()+Mg17 Al12 , forming the divorced
eutectic structure of [Mg()+Mg17 Al12 ] as shown in Fig.
1(a).
3.4 Mechanical properties
The mechanical properties of the alloys with and without
Sb and microaddition of RE are compared in Table 2. It can
be seen that Sb and RE microaddition to the alloy (SJTUHM1) resulted in benecial inuence on improving the
mechanical properties. It shows that the Sb- and REcontaining alloys have improved yield strength, ultimate
tensile strength, elongation and apparent fracture toughness
over the base alloy. It is obvious that the improvement of
tensile strength was ascribed to three aspects: (1) small grain
strengthening, (2) the change of morphology of Mg2 Si from
Chinese-script type to polygonal type, since long cracks can
easily nucleate along the interface between Chinese-script
Mg2 Si particles and Mg matrix, and (3) the dispersion
strengthening of ne particles (Mg2 Si and Mg3 Sb2 ).
In addition, owing to its high melting point (1228 C) of
those Mg3 Sb2 particles which can not act as nucleus of Mg2 Si
in Mg5Al1Zn1Si are also eective strengthening phases
for Mg alloy application at elevated temperatures,7) which
may be contributed to the improvement of tensile strength at
elevated temperatures.
3.5 Creep behavior
Figure 5 is several typical creep strain vs. time curves
obtained from the constant-load and constant-temperature
test (200 C/50 MPa) for the four kinds of alloys. The
460
Y. Guangyin, L. Manping, D. Wenjiang and A. Inoue
4000
1
1
2000
1000
1Mg
2Mg 2 Si
3Mg 3 Sb 2
4Mg 17 Al12
3000
CPS
5000
4
4
3
2
3
0
20
24
28
32
36
40
44
48
52
56
60
64
3
68
72
Fig. 2
X-ray diraction patterns of as-cast Mg5Al1Zn1Si0.5Sb alloy.
Fig. 3 Crystallization nuclei observing shows (a) SEI of Mg2 Si particles in

permanent mould cast Mg5Al1Zn1Si0.5Sb alloy (b) EDS spectrum
from the nucleus area A in (a).
Fig. 1 Optical micrographs showing the eect of Sb addition on the

microstructure of alloys; (a) as-cast Mg5Al1Zn1Si alloy, (b) solution
heat-treated Mg5Al1Zn1Si alloy, (c) solution heat-treated Mg5Al
1Zn1Si0.5Sb alloy.
simultaneous additions of Sb and mischmetal (MM) to Mg

5Al1ZnSi alloy reduced the steady state creep rate
signicantly. Moreover, the creep strain for the alloys after
100 hours decreased from 5.2% for Mg5Al1Zn1Si to
2.6% for SJTU-HM1, even lower than that of AE42 (2.7%). It
showed that tensile creep property of the newly developed
SJTU-HM1 alloy is better than that of AE42 alloy, which is
the benchmark creep-resistant magnesium die casting alloy
for automobile powertrain application.

10
606C(start of Mg2Si precipiation and Mg() nucleation)

616C(Start of Mg() nucleation:L-->Mg()+L)
600
500
407C(divorced eutectic reaction:

L-->Mg()+Mg17Al12)
400
Creep Strain, /%
700
Temperature, T/C
461
Mg-5Al-1Zn
Mg-4Al-3.0RE-0.2Mn(AE42)
Mg-5Al-1Zn-1Si
Mg-5Al-1Zn(AZ51)
SJTU-HM1
300
0
0
SJTU-HM1
20
1000s
200
60
80
100
Fig. 5 Creep curves of alloys at 200 C, 50 MPa.
Solidification Time, t /s
Fig. 4
40
Creep Time, t /h
Solidication cooling curves for alloys studied.
Table 2
Mechanical properties of permanent mould-cast MgAlZnSiX alloys.

150 C tensile
RT tensile
Alloy
Apparent fracture
Ulti.
Yield.
Elong.
Ulti.
Yield.
Elong.
toughness
(MPa)
(MPa)
(%)
(MPa)
(MPa)
(%)
Ak (J)
SJTU-HM1
235
108
178
99
14
28
AE42
AZ91
202
234
97
110
12
3
165
175
91
96
22
20
20
15
3.6 Corrosion resistance properties

Figure 6 shows the salt spray corrosion test result of the
alloys. Si shows an adverse eect on corrosion properties.
Single addition of Sb shows a similar eect like Si. On the
other hand, with both additions of Sb and MM microaddition,
SJTU-HM1 shows higher corrosion resistance than those of
AZ51 and AE42 alloys. This showed that Misch metal (Ce,
La, Nd, Pr) improved the corrosion resistance for MgAl
based alloys in chloride solutions. The solubility of rare
earths in the magnesium matrix is limited in the presence of
aluminum, but the intermetallic Al-RE phase formed is
electrochemically passive and does not aect the corrosion
rate much.8) The high corrosion resistance of the STJU-HM1
appears to be related to a certain positive synergism of
aluminum and RE elements in the aluminum rich zones along
R/mg. cm-2. d-1
1.2
1.0
0.8
Corrosion Rate,
0.6
0.4
0.2
0.0
AZ51
Mg-5Al-1Zn-1Si
AE42
SJTU-HM1
Alloy Code
Fig. 6 Corrosion rate compared with standard die casting alloys.
the grain boundaries, impeding the propagation of localized

corrosion attack. The improved passivity of SJTU-HM1
under the conditions is possibly due to the enrichment of
trace amounts of RE in the oxide lm. Further investigation is
under way.
4.
Summary
Microstructure and mechanical properties and corrosion

resistance for the developed SJTU-HM1 alloy were investigated and summarized as follows:
(1) Addition of Sb was found to be ecient in rening the
microstructure of the Mg5Al1Zn1Si-base alloy. The
morphology of Mg2 Si particles changed from coarse
Chinese-script shape to small polygonal type. The
modication mechanism of Sb is the formation of the
polygonal type Mg2 Si particles nucleate from Mg3 Sb2
particles.
(2) Rened microstructure in the modied alloy by
simultaneous additions of Sb and mischmetal results
in signicant improvement in tensile properties and
toughness, creep resistance at high temperatures as
compared to the base alloy of Mg5Al1Zn1Si. The
mechanical properties at room temperature are similar
to or better than those of AZ91 alloy and the high
temperature properties are even better than those of
AE42 alloy.
(3) With simultaneous additions of Sb and mischmetal, the
corrosion resistance of the Si-containing Mg alloy is
improved signicantly and even better than that of
AE42 alloy.
462
Y. Guangyin, L. Manping, D. Wenjiang and A. Inoue
Acknowledgements
One of the authors (Yuan Guangyin) would like to thank
the Japanese Society for the Promotion of Science (JSPS) for
providing support to publish the present work.
REFERENCES
1) P. Humble: Mater. Forum. 21 (1997) 4556.
2) Yuan Guangyin, Wang Qudong and Ding Wenjiang: J. Mater. Sci. 37
(2002) 127132.
3) G. H. Li, H. S. Gill and R. A. Varin: Metall. Trans. A. 24A (1993) 2383
2387.
4) J. J. Kim, D. H. Kim, K. S. Shin and N. J. Kim: Scr. Mater. 41 (1999)
333340.
5) G. Y. Yuan, Z. L. Liu, Q. D. Wang and W. J. Ding: Mater. Lett. 56
(2002) 5358.
6) B. L. Bramt: Metall. Trans. 6 (1971) 12581263.
7) Yuan Guangyin, Sun Yangshan and Ding Wenjiang: Scr. Mater. 43
(2000) 10091013.
8) O. Lunder and K. Nisancioglu: Progress in the understanding and
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Materials Transactions, Vol. 44, No. 4 (2003) pp.

Mechanical Properties and Microstructure of MgAlZnSi-base Alloy

The growing demand for more fuel-ecient vehicles to

whom correspondence should be addressed. Current address: Inoue

ment should be achieved.

Three alloys of which the compositions are listed in

Mechanical Properties and Microstructure of MgAlZnSi-base Alloy

Chemical composition of the alloys (mass%).

Grain size (mm)

Results and Discussion

3.3 Solidication process of MgAlZnSi-base alloys

Y. Guangyin, L. Manping, D. Wenjiang and A. Inoue

X-ray diraction patterns of as-cast Mg5Al1Zn1Si0.5Sb alloy.

Fig. 3 Crystallization nuclei observing shows (a) SEI of Mg2 Si particles in

Fig. 1 Optical micrographs showing the eect of Sb addition on the

simultaneous additions of Sb and mischmetal (MM) to Mg

Mechanical Properties and Microstructure of MgAlZnSi-base Alloy

606C(start of Mg2Si precipiation and Mg() nucleation)

407C(divorced eutectic reaction:

Fig. 5 Creep curves of alloys at 200 C, 50 MPa.

Solidication cooling curves for alloys studied.

Mechanical properties of permanent mould-cast MgAlZnSiX alloys.

3.6 Corrosion resistance properties

R/mg. cm-2. d-1

Fig. 6 Corrosion rate compared with standard die casting alloys.

the grain boundaries, impeding the propagation of localized

Microstructure and mechanical properties and corrosion

Y. Guangyin, L. Manping, D. Wenjiang and A. Inoue

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